The invention relates to novel substituted sulfonylamino(thio)carbonyl compounds, to a plurality of processes and to novel intermediates for preparing them, and to their use as herbicides.
It is already known that certain sulfonylaminocarbonyl compounds have herbicidal properties (cf. EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266, DE 4029753). The action of these compounds, however, is not satisfactory in every respect.
This invention, then, provides the novel sulfonylamino(thio)carbonyl compounds of the general formula (I) 
in which
n represents the numbers 0, 1 or 2,
A represents a single bond, or oxygen or sulfur, or the grouping Nxe2x80x94R, in which R represents hydrogen, alkyl, alkenyl, alkinyl or cycloalkyl,
Q represents oxygen or sulfur,
R1 represents hydrogen or formyl or represents respectively optionally substituted alkyl, alkoxy, alkylamino, alkoxyamino, dialkylamino, N-alkoxy-N-alkyl-amino, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, alkenyl, alkinyl, cycloalkyl, cycloalkylcarbonyl or cycloalkylsulfonyl,
R2 represents cyano or halogen or represents respectively optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylaminosulfonyl, alkenyl, alkinyl, alkenyloxy or alkinyloxy, and
R3 represents respectively optionally substituted heterocyclyl having 5 ring members of which at least one is oxygen, sulfur or nitrogen and from one to three further ring members can be nitrogen,
and salts of compounds of the formula (I).
The novel substituted sulfonylamino(thio)carbonyl compounds of the general formula (I) are obtained by reacting
(a) aminosulfonyl compounds of the general formula (II) 
xe2x80x83in which
n, A, R1 and R2 are each as defined above
with (thio)carboxylic acid derivatives of the general formula (III) 
xe2x80x83in which
Q and R3 are each as defined above and
Z represents halogen, alkoxy, aryloxy or arylalkoxy,
optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or
(b) sulfonyl iso(thio)cyanates of the general formula (IV) 
xe2x80x83in which
n, A, Q, R1 and R2 are each as defined above
with heterocycles of the general formula (V)
Hxe2x80x94R3xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3 is as defined above,
optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent, or
(c) chlorosulfonyl compounds of the general formula (VI) 
xe2x80x83in which
n, A, R1 and R2 are each as defined above
with heterocycles of the general formula (V)
Hxe2x80x94R3xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3 is as defined above
and metal (thio)cyanates of the general formula (VII)
MQCNxe2x80x83xe2x80x83(VII)
xe2x80x83in which
Q is as defined above,
optionally in the presence of a reaction auxiliary and optionally in the presence of a diluent, or
(d) chlorosulfonyl compounds of the general formula (VI) 
xe2x80x83in which
n, A, R1 and R2 are each as defined above,
with (thio)carboxamides of the general formula (VIII) 
xe2x80x83in which
Q and R3 are each as defined above,
optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or
(e) sulfonylamino(thio)carbonyl compounds of the general formula (IX) 
xe2x80x83in which
n, A, Q, R1 and R2 are each as defined above and
Z represents halogen, alkoxy, aryloxy or arylalkoxy,
with heterocycles of the general formula (V)
Hxe2x80x94R3xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3 is as defined above,
optionally in the presence of an acid acceptor and optionally in the presence of a diluent, or
(f) heterocycles of the general formula (V)
Hxe2x80x94R3xe2x80x83xe2x80x83(V)
xe2x80x83in which
R3 is as defined above,
with chlorosulfonyl iso(thio)cyanate, optionally in the presence of a diluent, and reacting the adducts formed in this reaction in situ with benzene derivatives of the general formula (X) 
xe2x80x83in which
n, A, R1 and R2 are each as defined above,
optionally in the presence of an acid acceptor and optionally in the presence of a diluent,
and converting, if desired, the compounds of the formula (I) obtained by processes (a), (b), (c), (d), (e) or (f) by customary methods into salts.
The novel substituted sulfonylamino(thio)carbonyl compounds of the general formula (I) have strong herbicidal activity.
The invention preferably provides compounds of the formula (I) in which
n represents the numbers 0, 1 or 2,
A represents a single bond, or oxygen or sulfur, or the grouping Nxe2x80x94R, in which R represents hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkinyl or C3-C6-cycloalkyl,
Q represents oxygen or sulfur,
R1 represents hydrogen or formyl or represents respectively optionally cyano-, fluoro-, chloro-, bromo-, phenyl- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylamino, alkoxyamino, dialkylamino, N-alkoxy-N-alkyl-amino, alkylcarbonyl, alkoxycarbonyl, alkylsulfonyl, alkenyl or alkinyl having in each case up to 6 carbon atoms, or represents respectively optionally cyano-, fluoro-, chloro-, bromo- or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C3-C6-cycloalkyl-carbonyl or C3-C6-cycloalkyl-sulfonyl,
R2 represents cyano, fluoro, chloro or bromo or represents respectively optionally cyano-, fluoro-, chloro-, bromo- or C1-C4-alkoxy-substituted alkyl, alkoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, dialkylaminosulfonyl, alkenyl, alkinyl, alkenyloxy or alkinyloxy having in each case up to 6 carbon atoms, and
R3 represents respectively optionally substituted heterocyclyl of the formulae below, 
xe2x80x83in which
Q1, Q2 and Q3 each represent oxygen or sulfur, and
R4 represents hydrogen, hydroxyl, amino or cyano, or represents C2-C10-alkylideneamino, or represents optionally fluoro-, chloro-, bromo-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, or represents respectively optionally fluoro-, chloro- and/or bromo-substituted C2-C6-alkenyl or C2-C6-alkinyl, or represents respectively optionally fluoro-, chloro-, bromo-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylamino or C1-C6-alkyl-carbonylamino, or represents C3-C6-alkenyloxy, or represents di-(C1-C4-alkyl)-amino, or represents respectively optionally fluoro-, chloro-, bromo-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C3-C6-cycloalkylamino or C3-C6-cycloalkyl-C1-C4-alkyl, or represents respectively optionally fluoro-, chloro-, bromo-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl- and/or C1-C4-alkoxy-substituted phenyl or phenyl-C1-C4-alkyl,
R5 represents hydrogen, hydroxyl, mercapto, amino, cyano, fluoro, chloro, bromo or iodo, or represents optionally fluoro-, chloro-, bromo-, cyano-, C1-C4-alkoxy-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkyl, or represents respectively optionally fluoro-, chloro- and/or bromo-substituted C2-C6-alkenyl or C2-C6-alkinyl, or represents respectively optionally fluoro-, chloro-, cyano-, C1-C4-alkoxy- or C1-C4-alkoxy-carbonyl-substituted C1-C6-alkoxy, C1-C6-alkylthio, C1-C6-alkylamino or C1-C6-alkylcarbonylamino, or represents C3-C6-alkenyloxy, C3-C6-alkinyloxy, C3-C6-alkenylthio, C3-C6-alkinylthio, C3-C6-alkenylamino or C3-C6-alkinylamino, or represents di-(C1-C4-alkyl)-amino, or represents respectively optionally methyl- and/or ethyl-substituted aziridino, pyrrolidino, piperidino or morpholino, or represents respectively optionally fluoro-, chloro-, bromo-, cyano- and/or C1-C4-alkyl-substituted C3-C6-cycloalkyl, C5-C6-cycloalkenyl, C3-C6-cycloalkyloxy, C3-C6-cycloalkylthio, C3-C6-cycloalkylamino, C3-C6-cycloalkyl-C1-C4-alkyl, C3-C6-cycloalkyl-C1-C4-alkoxy, C3-C6-cycloalkyl-C1-C4-alkylthio or C3-C6-cycloalkyl-C1-C4-alkylamino, or represents respectively optionally fluoro-, chloro-, bromo-, cyano-, nitro-, C1-C4-alkyl-, trifluoromethyl-, C1-C4-alkoxy- and/or C1-C4-alkoxy-carbonyl-substituted phenyl, phenyl-C1-C4-alkyl, phenoxy, phenyl-C1-C4-alkoxy, phenylthio, phenyl-C1-C4-alkylthio, phenylamino or phenyl-C1-C4-alkylamino, or
R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, and
R6, R7 and R8 are identical or different and each represent hydrogen, cyano, fluoro, chloro, bromo, or represent respectively optionally fluoro-, chloro-, bromo- or C1-C4-alkoxy-substituted alkyl, alkenyl, alkinyl, alkoxy, alkenyloxy, alkinyloxy, alkylthio, alkenylthio, alkinylthio, alkylsulfinyl or alkylsulfonyl having in each case up to 6 carbon atoms, or represent optionally cyano-, fluoro-, chloro-, bromo- or C1-C4-alkyl-substituted cycloalkyl having 3 to 6 carbon atoms.
The invention further preferably provides the sodium, potassium, magnesium, calcium, ammonium, C1-C4-alkyl-ammonium, di-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-ammonium, tetra-(C1-C4-alkyl)-ammonium, tri-(C1-C4-alkyl)-sulfonium, C5- or C6-cycoalkyl-ammonium and di-(C1-C2-alkyl)-benzyl-ammonium salts of compounds of the formula (I) in which n, A, Q, R1, R2 and R3 each have the meanings indicated. above as preferred.
The invention relates in particular to compounds of the formula (I) in which
n represents the numbers 0, 1 or 2,
A represents a single bond, or oxygen or the grouping Nxe2x80x94R, in which R represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, propenyl, butenyl, propinyl, butinyl, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
Q represents oxygen or sulfur,
R1 represents hydrogen or formyl, or represents respectively optionally fluoro-, chloro-, bromo-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, methoxyamino, ethoxyamino, n- or i-propoxyamino, n-, i-, s- or t-butoxyamino, dimethylamino, diethylamino, N-methoxy-N-methyl-amino, acetyl, propionyl, butyroyl, methoxycarbonyl, ethoxycarbonyl, n- or i-propoxycarbonyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, n-, i-, s- or t-butylsulfonyl, propenyl, butenyl, propinyl or butinyl, or represents respectively optionally fluoro-, chloro- or methyl-substituted cyclopropyl, cyclopropylcarbonyl or cyclopropylsulfonyl,
R2 represents cyano, fluoro, chloro or bromo, or represents respectively optionally fluoro-, chloro-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i- or s-butyl, methoxy, ethoxy, n- or i-propoxy, n-, i- or s-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, dimethylaminosulfonyl or diethylaminosulfonyl, or represents propenyl, butenyl, propinyl, butinyl, propenyloxy, butenyloxy, propinyloxy or butinyloxy, and
R3 represents respectively optionally substituted heterocyclyl of the formulae below: 
xe2x80x83in which
Q1, Q2 and Q3 each represent oxygen or sulfur, and
R4 represents hydrogen, hydroxyl or amino, or represents C3-C8-alkylideneamino, or represents respectively optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents respectively optionally fluoro-, chloro- or bromo-substituted propenyl, butenyl, propinyl or butinyl, or represents respectively optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, or represents propenyloxy or butenyloxy, or represents dimethylamino or diethylamino, or represents respectively optionally fluoro-, chloro-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, or represents respectively optionally fluoro-, chloro-, methyl-, trifluoromethyl- and/or methoxy-substituted phenyl or benzyl,
R5 represents hydrogen, hydroxyl, mercapto, amino, fluoro, chloro or bromo, or represents respectively optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents respectively optionally fluoro-, chloro- or bromo-substituted ethenyl, propenyl, butenyl, propinyl or butinyl, or represents respectively optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylamino, ethylamino, n- or i-propylamino, n-, i-, s- or t-butylamino, or represents propenyloxy, butenyloxy, propinyloxy, butinyloxy, propenylthio, propadienylthio, butenylthio, propinylthio, butinylthio, propenylamino, butenylamino, propinylamino or butinylamino, or represents dimethylamino, diethylamino or dipropylamino, or represents respectively optionally fluoro-, chloro-, methyl- and/or ethyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentenyl, cyclohexenyl, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, cyclopropylamino, cyclobutylamino, cyclopentylamino, cyclohexylamino, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylmethoxy, cyclobutylmethoxy, cyclopentylmethoxy, cyclohexylmethoxy, cyclopropylmethylthio, cyclobutylmethylthio, cyclopentylmethylthio, cyclohexylmethylthio, cyclopropylmethylamino, cyclobutylmethylamino, cyclopentylmethylamino or cyclohexylmethylamino, or represents respectively optionally fluoro-, chloro-, methyl-, trifluoromethyl-, methoxy- and/or methoxycarbonyl-substituted phenyl, benzyl, phenoxy, benzyloxy, phenylthio, benzylthio, phenylamino or benzylamino, or
R4 and R5 together represent optionally branched alkanediyl having 3 to 11 carbon atoms, furthermore
R6, R7 and R8 are identical or different and each represent hydrogen, cyano, fluoro, chloro or bromo, or represent respectively optionally fluoro-, chloro-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, propenyl, butenyl, propinyl, butinyl, methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, propenyloxy, butenyloxy, propinyloy, butinyloxy, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, propenylthio, butenylthio, propinylthio, butinylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, or represent cyclopropyl.
A very particularly preferred group of compounds according to the invention are those compounds of the formula (I) in which
n represents the numbers 0, 1 or 2,
A represents a single bond,
Q represents oxygen or sulfur,
R1 represents respectively optionally fluoro- and/or chloro-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
R2 represents fluoro, chloro or bromo, or represents respectively optionally fluoro-, and/or chloro-substituted methyl, ethyl, methoxy, ethoxy, methylthio or ethylthioxe2x80x94in each case in position 6-, and
R3 represents optionally substituted triazolinyl of the formula below, 
xe2x80x83in which
Q1 represents oxygen or sulfur, and
R4 represents respectively optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents propenyl or propinyl, or represents methoxy, ethoxy, n- or i-propoxy, or represents cyclopropyl, and
R5 represents hydrogen, chloro or bromo, or represents respectively optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents respectively optionally fluoro- and/or chloro-substituted propenyl or propinyl, or represents respectively optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, or represents propenyloxy or cyclopropyl.
Q represents oxygen or sulfur,
R1 represents respectively optionally fluoro- and/or chloro-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
R2 represents fluoro, chloro or bromo, or represents respectively optionally fluoro- and/or chloro-substituted methyl, ethyl, methoxy, ethoxy, methylthio or ethylthioxe2x80x94in each case in position 6-, and
R3 represents optionally substituted triazolinyl of the formula below, 
xe2x80x83in which
Q1 represents oxygen or sulfur, and
R4 represents respectively optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents propenyl or propynyl, or represents methoxy, ethoxy, n- or i-propoxy, or represents cyclopropyl, and
R5 represents hydrogen, chloro or bromo, or represents respectively optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, or represents respectively optionally fluoro- and/or chloro-substituted propenyl or propinyl, or represents respectively optionally fluoro-, chloro-, cyano-, methoxy- or ethoxy-substituted methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, or represents propenyloxy or cyclopropyl.
The radical definitions listed above, whether general or listed in ranges of preference, apply not only to the end products of the formula (I) but also, correspondingly, to the starting materials and/or intermediates required in each case for the preparation. These radical definitions can be combined as desired with one another, thus including combinations between the preferred ranges indicated.
Using, for example, 2-fluoro-6-methylthio-benzenesulfonamide and 5-ethoxy4-methyl-2-phenoxycarbonyl-2,4-dihydro-3H-1,2,4-triazole-3-thione as starting materials, the course of reaction in the process (a) according to the invention can be illustrated by the following equation: 
Using, for example, 2-ethylthio-6-methyl-phenylsulfonyl isothiocyanate and 5-ethyl-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of reaction in the process (b) according to the invention can be illustrated by the following equation: 
Using, for example, 2-methylthio-3-methyl-benzenesulfonyl chloride, 5-ethyl-thio-4-methoxy-2,4-dihydro-3H-1,2,4-triazol-3-one and potassium cyanate as starting materials, the course of reaction in the process (c) according to the invention can be illustrated by the following equation: 
Using, for example, 2-ethylthio-4-fluoro-benzenesulfonyl chloride and 5-methyl-1,2,4-oxadiazole-3-carboxamide as starting materials, the course of reaction in the process (d) according to the invention can be illustrated by the following equation: 
Using, for example, N-(2-chloro-6-propylthio-phenylsulfonyl)-O-methylurethane and 4-methyl-5-methylthio-2,4-dihydro-3H-1,2,4-triazol-3-one as starting materials, the course of reaction in the process (e) according to the invention can be illustrated by the following equation: 
Using, for example, 5-chloro-4-ethyl-2,4-dihydro-3H-1,2,4-triazol-3-one and chlorosulfonyl isocyanate and then 2-ethylthio-6-methyl-aniline as starting materials, the course of reaction in the process (f) according to the invention can be illustrated by the following equation: 
A general definition of the aminosulfonyl compounds to be used as starting materials in the process (a) according to the invention for the preparation of compounds of the formula (I) is given by the formula (II). In the formula (II), n, A, R1 and R2 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferable or, respectively, particularly preferable for n, A, R1 and R2.
With the exception of the compound 2,6-bis-methylthio-benzenesulfonamide (cf. EP 135332, U.S. Pat. No. 4,604,131), the starting materials of the formula (II) have to date not been disclosed in the literature; with the exception of 2,6-bis-methylthio-benzenesulfonamide, they are novel substances and likewise form part of the subject matter of the present application.
The novel aminosulfonyl compounds of the formula (II) in which n represents zero, A represents a single bond and R1 represents respectively optionally substituted alkyl, alkenyl, alkinyl or cycloalkyl are obtained when t-butylaminosulfonyl compounds of the general formula (XI) 
in which
A and R2 are each as defined above
are metallatedxe2x80x94i.e. the hydrogen atom shown in the formula (XI) is replaced by a metal atomxe2x80x94with an organometallic compound, such as for example butyllithium in hexane, if appropriate in the presence of a (further) inert diluent, such as for example tetrahydrofuran, and under an inert gas atmosphere, such as for example under argon, at temperatures between xe2x88x9250xc2x0 C. and +20xc2x0 C., and then, in the same reaction medium, reacted with sulfur at temperatures between xe2x88x9230xc2x0 C. and +30xc2x0 C.xe2x80x94i.e. the metal atom is replaced by sulfurxe2x80x94, and then, in the same reaction medium, reacted with an alkylating agent of the general formula (XII)
X1xe2x80x94R1xe2x80x83xe2x80x83(XII)
xe2x80x83in which
R1 represents respectively optionally substituted alkyl, alkenyl, alkinyl or cycloalkyl and
X1 represents halogen, preferably chlorine, bromine or iodine
at temperatures between 0xc2x0 C. and 100xc2x0 C., and the thus-obtained t-butylaminosulfonyl compounds of the general formula (XIII) 
xe2x80x83in which
A, R1 and R2 are each as defined above
are thenxe2x80x94preferably after intermediate isolationxe2x80x94reacted with a strong acid, such as for example trifluoroacetic acid, if appropriate in the presence of a diluent, such as for example methylene chloride, at temperatures between 0xc2x0 C. and 50xc2x0 C. (cf. the preparation examples).
The novel compounds of the formula (II) in which n represents zero, A represents a single bond and R1 represents H are obtained when the t-butylaminosulfonyl compounds of the general formula (XI) are, as described above, reacted with sulfur after metallation, and the product formed of the general formula (XIV) 
in which
A and R2 are each as defined above
is thenxe2x80x94if appropriate after intermediate isolationxe2x80x94reacted with a strong acid, such as for example trifluoroacetic acid, if appropriate in the presence of a diluent, such as for example methylene chloride, at temperatures between 0xc2x0 C. and 50xc2x0 C., and the thus-obtained isomerization product of the general formula (XV) 
xe2x80x83in which
A and R2 are each as defined above
isxe2x80x94if appropriate after intermediate isolationxe2x80x94reacted with a Lewis acid, such as for example boron(III)bromide, in the presence of a diluent, such as for example methylene chloride, at temperatures between 0xc2x0 C. and 50xc2x0 C. (cf. the preparation examples).
The novel compounds of the formula (II) in which n represents zero, A represents a single bond and R1 represents hydrogen or respectively optionally substituted alkyl, alkenyl, alkinyl or cycloalkyl are obtained when the t-butylaminosulfonyl compounds of the general formula (XI) are, as described above, reacted with sulfur after metallation, and the products formed of the general formula (IV)xe2x80x94abovexe2x80x94are thenxe2x80x94if appropriate after intermediate isolationxe2x80x94reacted with a suitable oxidizing agent, such as for example dimethyl sulfoxide, at temperatures between 20xc2x0 C. and 120xc2x0 C., and the disulfides formed of the general formula (XVI) 
in which
A and R2 are each as defined above
are thenxe2x80x94if appropriate after intermediate isolationxe2x80x94reacted with a strong acid, such as for example trifluoroacetic acid, if appropriate in the presence of a diluent, such as for example methylene chloride, at temperatures between 0xc2x0 C. and 50xc2x0 C., and the disulfides formed of the general formula (XVII) 
xe2x80x83in which
A and R2 are each as defined above
are thenxe2x80x94if appropriate after intermediate isolationxe2x80x94reacted with a reducing agent, such as for example sodium tetrahydridoborate (sodium borohydride), if appropriate in the presence of a diluent, such as for example methanol, at temperatures between 0xc2x0 C. and 50xc2x0 C., and the thus-obtained compounds of the formula (II) in which R1 represents hydrogen are then, if appropriate, reacted with an alkylating agent of the general formula (XII)
X1xe2x80x94R1xe2x80x83xe2x80x83(XII)
xe2x80x83in which
R1 represents respectively optionally substituted alkyl, alkenyl, alkinyl or cycloalkyl and
X1 represents halogen, preferably chlorine, bromine or iodine at temperatures between 0xc2x0 C. and 100xc2x0 C. (cf. the preparation examples).
The novel aminosulfonyl compounds of the formula (II) in which A represents a single bond, R1 represents respectively optionally substituted alkyl, alkenyl, alkinyl or cycloalkyl and R2 represents respectively optionally substituted alkyl, alkenyl or alkinylxe2x80x94in position 6xe2x80x94are obtained when t-butylaminosulfonyl compounds of the general formula (XVIII) 
in which
A is as defined above
are metallatedxe2x80x94i.e. the hydrogen atom shown in the formula (XVIII) is replaced by a metal atomxe2x80x94with a metalloorganic compound, such as for example butyllithium in hexane, if appropriate in the presence of a (further) inert diluent, such as for example tetrahydrofuran, and under an inert gas atmosphere, such as for example argon, at temperatures between xe2x88x9250xc2x0 C. and +20xc2x0 C., and then, in the same reaction medium, reacted with sulfurxe2x80x94i.e. the metal atom is replaced by sulfurxe2x80x94at temperatures between xe2x88x9230xc2x0 C. and +30xc2x0 C., and then, in the same reaction medium, reacted with an alkylating agent of the general formula (XII)
X1xe2x80x94R1xe2x80x83xe2x80x83(XII)
xe2x80x83in which
R1 represents respectively optionally substituted alkyl, alkenyl, alkinyl or cycloalkyl and
X1 represents halogen, preferably chlorine, bromine or iodine
at temperatures between 0xc2x0 C. and 100xc2x0 C. and the thus-obtained t-butylaminosulfonyl compounds of the general formula (XIX) 
xe2x80x83in which
A and R1 are each as defined above,
are thenxe2x80x94preferably after intermediate isolationxe2x80x94metallated with an organometallic compound, such as for example butyllithium in hexane, if appropriate in the presence of a (further) inert diluent, such as for example tetrahydrofuran, and under an inert gas atmosphere, such as for example under argon, at temperatures between xe2x88x9250xc2x0 C. and +20xc2x0 C. and then, in the same reaction medium, reacted with an alkylating agent of the general formula (XX)
X2xe2x80x94R2xe2x80x83xe2x80x83(XX)
xe2x80x83in which
R2 represents respectively optionally substituted alkyl, alkenyl or alkinyl and
X2 represents halogen, preferably chloro, bromo or iodo at temperatures between 0xc2x0 C. and 100xc2x0 C. (cf. the preparation examples).
The compounds of the formula (II) in which n represents zero can be converted in a conventional manner into the corresponding compounds of the formula (II) in which n represents 1 or 2 by reaction with suitable oxidizing agents, such as for example 3-chloro-perbenzoic acid (cf. the preparation examples).
Some of the n-butylaminosulfonyl compounds of the formula (XIV)xe2x80x94abovexe2x80x94required as precursors can also be obtained by reacting suitable disulfides of the formula (XVI)xe2x80x94abovexe2x80x94with suitable alkylating agents of the formula (XII)xe2x80x94abovexe2x80x94in the presence of sodium hydroxymethanesulfinate dihydrate and in the presence of disodium hydrogen phosphate and in the presence of a diluent, such as for example N,N-dimethyl-formamide (cf. the preparation examples).
A general definition of the (thio)carboxylic acid derivatives also to be used as starting materials in the process (a) according to the invention for the preparation of compounds of the formula (I) is given by the formula (III). In the formula (III), Q and R3 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferable or, respectively, particularly preferable for Q and R3; Z preferably represents fluoro, chloro, bromo, C1-C4-alkoxy, phenoxy or benzyloxy, and in particular chloro, methoxy, ethoxy or phenoxy.
The starting materials of the formula (III) are known and/or can be prepared by methods known per se (cf. EP 459244, EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266).
A general definition of the sulfonyl iso(thio)cyanates to be used as starting materials in the process (b) according to the invention for the preparation of the compounds of the formula (I) is given by the formula (IV). In the formula (IV), n, A, Q, R1 and R2 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferable or particularly preferable for n, A, Q, R1 and R2.
With the exception of the compound 2,6-bis-methylthio-phenylsulfonyl isocyanate (cf. EP 135332), the starting materials of the formula (IV) have not to date been disclosed in the literature; with the exception of 2,6-bis-methylthio-phenylsulfonyl isocyanate, they are novel substances and likewise form part of the subject matter of the present application.
The novel sulfonyl iso(thio)cyanates of the formula (IV) are obtained when aminosulfonyl compounds of the general formula (II)xe2x80x94abovexe2x80x94are reacted with phosgene or thiophosgene, if appropriate in the presence of an alkyl isocyanate, such as for example butyl isocyanate, if appropriate in the presence of a reaction auxiliary, such as for example diazabicyclo[2.2.2]octane, and in the presence of a diluent, such as for example toluene, xylene or chlorobenzene, at temperatures between 80xc2x0 C. and 150xc2x0 C., and, after the reaction has ended, the volatile components are distilled off under reduced pressure.
A general definition of the heterocycles also to be used as starting materials in the processes (b), (c), (e) and (f) according to the invention for preparing the compounds of the formula (I) is given by the formula (V). In the formula (V), R3 preferably or in particular has that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferable or particularly preferable for R3.
The starting materials of the formula (V) are known and/or can be prepared by methods known per se (cf. EP 341489, EP 422469, EP 425948, EP 431291, EP 507171, EP 534266).
A general definition of the chlorosulfonyl compounds to be used as starting materials in the processes (c) and (d) according to the invention for preparing compounds of the formula (I) is given by the formula (VI). In the formula (VI), n, A, R1 and R2 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferable or particularly preferable for n, A, R1 and R2.
The starting materials of the formula (VI) have not to date been disclosed in the literature; as novel substances they are likewise part of the subject matter of the present application.
The novel chlorosulfonyl compounds of the formula (VI) are obtained when the corresponding amino compounds of the general formula (XXI) 
in which
A, R1 and R2 are as defined above are reacted with an alkali metal nitrite, such as for example sodium nitrite, in the presence of hydrochloric acid at temperatures between xe2x88x9210xc2x0 C. and +10xc2x0 C. and the diazonium salt solution thus obtained is reacted with sulfur dioxide in the presence of diluent, such as for example dichloromethane, 1,2-dichloro-ethane or acetic acid, and in the presence of a catalyst, such as for example copper(I)chloride and/or copper(II)chloride, at temperatures between xe2x88x9210xc2x0 C. and +50xc2x0 C.
A general definition of the (thio)carboxamides to be used as starting materials in the process (d) according to the invention for the preparation of the compounds of the formula (I) is given by the formula (VIII). In the formula (VIII), Q and R3 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferable or particularly preferable for Q and R3.
The starting materials of the formula (VIII) are known and/or can be prepared by methods known per se (cf. EP 459244).
A general definition of the sulfonylamino(thio)carbonyl compounds to be used as starting materials in the process (e) according to the invention for the preparation of the compounds of the formula (I) is given by the formula (IX). In the formula (IX), n, A, Q, R1 and R2 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferable or particularly preferable for n, A, Q, R1 and R2; Z preferably represents fluoro, chloro, bromo, C1-C4-alkoxy, phenoxy or benzyloxy, and in particular represents chloro, methoxy, ethoxy or phenoxy.
The starting materials of the formula (IX) are known and/or can be prepared by methods known per se.
A general definition of the benzene derivatives to be used as starting materials in the process (f) according to the invention for the preparation of the compounds of the formula (I) is given by the formula (X). In the formula (X), n, A, R1 and R2 preferably or in particular have that meaning which has already been indicated above, in connection with the description of the compounds of the formula (I) according to the invention, as being preferable or particularly preferable for n, A, R1 and R2.
The starting materials of the formula (X) are known and/or can be prepared by methods known per se.
The processes (a), (b), (c), (d), (e) and (f) according to the invention for the preparation of the novel compounds of the formula (I) are preferably carried out using diluents. Suitable diluents in this context are virtually all inert organic solvents. These include, preferably, aliphatic and aromatic, optionally halogenated hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylene chloride, ethylene chloride, chloroform, tetrachloromethane, chlorobenzene and o-dichlorobenzene; ethers such as diethyl ether and dibutyl ether, glycol dimethyl ether and diglycol dimethyl ether, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; esters such as methyl acetate and ethyl acetate; nitrites, for example acetonitrile and propionitrile; amides, for example dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric triamide.
Suitable reaction auxiliaries and/or acid acceptors for the processes (a), (b), (c), (d), (e) and (f) according to the invention are all acid-binding agents which are conventionally used for such reactions. Preference is given to alkali metal hydroxides, such as for example sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, such as for example calcium hydroxide, alkali metal carbonates and alkoxides, such as sodium carbonate and potassium carbonate, sodium tert-butoxide and potassium tert-butoxide, and also basic nitrogen compounds, such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisobutylamine, dicyclohexylamine, ethyldiisopropylamine, ethyldicyclohexylamine, N,N-dimethylbenzylamine, N,N-dimethyl-aniline, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 2-ethyl-, 4-ethyl- and 5-ethyl-2-methyl-pyridine, 1,5-diazabicyclo[4.3.0]-non-5-ene (DBN), 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU) and 1,4-diazabicyclo-[2.2.2]-octane (DABCO).
The reaction temperatures in the processes (a), (b), (c), (d), (e) and (f) according to the invention can be varied within a relatively wide range. The processes are in general carried out at temperatures of between xe2x88x9220xc2x0 C. and +150xc2x0 C., preferably at temperatures between 0xc2x0 C. and +100xc2x0 C.
The processes (a), (b), (c), (d), (e) and (f) according to the invention are generally carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.
For carrying out processes (a), (b), (c), (d), (e) and (f) according to the invention, the starting materials required in each case are in general employed in approximately equimolar quantities. However, it is also possible to use one of the components employed in each case in a relatively large excess. The reactions are in general carried out in a suitable diluent in the presence of an acid acceptor, and the reaction mixture is stirred for a number of hours at the particular temperature required. Work-up in the case of the processes (a), (b), (c), (d), (e) and (f) according to the invention is in each case carried out by customary methods (cf. the Preparation Examples).
Salts of the compounds of the general formula (I) according to the invention can be prepared if desired. Such salts are obtained in a simple manner by customary methods of forming salts, for example by dissolving or dispersing a compound of the formula (I) in an appropriate solvent, for example methylene chloride, acetone, tert-butyl methyl ether or toluene, and adding an appropriate base. The salts can thenxe2x80x94if desired after prolonged stirringxe2x80x94be isolated by concentration or filtration with suction.
The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and, especially, as weed-killers. By weeds, in the broadest sense, there are to be understood all plants which grow in locations where they are not wanted. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in connection with the following plants:
Dicotyledonous Weeds of the Genera
Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous Cultures of the Genera
Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous Weeds of the Genera
Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledonous Cultures of the Genera
Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.
The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for controlling weeds in perennial cultures, for example afforestations, decorative tree plantings, orchards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, in lawns, turf and pasture-land, and for the selective control of weeds in annual cultures.
The compounds of the formula (I) according to the invention are suitable for controlling monocotyledonous and dicotyledonous weeds, both pre-emergence and post-emergence. They exhibit strong herbicidal action and a broad spectrum of activity when used on the soil and on aerial parts of the plants.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, soluble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-formning agents.
In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaplthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, as well as water.
Suitable solid carriers are:
for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and silicates, suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; suitable emulsifying and/or foam-forming agents are: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates as well as protein hydrolyzates; suitable dispersing agents are: for example lignin-sulfite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latexes, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, finished formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example anilides, such as diflufenican and propanil; arylcarboxylic acids, such as dichloropicolinic acid, dicamba and picloram; aryloxyalkanoic acids, such as 2,4-D, 2,4-DB, 2,4-DP, fluroxypyr, MCPA, MCPP and triclopyr; aryloxy-phenoxy-alkanoic esters, such as diclofop-methyl, fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl and quizalofop-ethyl; azinones, such as chloridazon and norflurazon; carbamates, such as chlorpropham, desmedipham, phenmedipham and propham; chloroacetanilides, such as alachlor, acetochlor, butachlor, metazachlor, metolachlor, pretilachlor and propachlor; dinitroanilines, such as oryzalin, pendimethalin and trifluralin; diphenyl ethers, such as acifluorfen, bifenox, fluoroglycofen, fomesafen, halosafen, lactofen and oxyfluorfen; ureas, such as chlorotoluron, diuron, fluometuron, isoproturon, linuron and methabenzthiazuron; hydroxylamines, such as alloxydim, clethodim, cycloxydim, sethoxydim and tralkoxydim; imidazolinones, such as imazethapyr, imazarnethabenz, imazapyr and imazaquin; nitriles, such as bromoxynil, dichlobenil and ioxynil; oxyacetamides, such as mefenacet; sulfonylureas, such as amidosulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuiron, metsulfuron-methyl, nicosulfuron, primisulfuron, pyrazosulfiron-ethyl, thifensulfuron-methyl, triasulfuron and tribenuron-methyl; thiocarbamates, such as butylate, cycloate, diallate, EPTC, esprocarb, molinate, prosulfocarb, thiobencarb and triallate; triazines, such as atrazine, cyanazine, simazine, simetryne, terbutryne and terbutylazine; triazinones, such as hexazinone, metamitron and metribuzin; and others, such as aminotriazole, benfuresate, bentazone, cinimethylin, clomazone, clopyralid, difenzoquat, dithiopyr, ethoflimesate, fluorochloridone, glufosinate, glyphosate, isoxaben, pyridate, quinchlorac, quinmerac, sulphosate and tridiphane.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by fisher dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.
The preparation and use of the active compounds according to the invention can be seen from the following examples.